Combustion

COMBUSTION
Combustion is a chemical reaction in which certain element of the fuel combine with oxygen and releasing a large quantity of energy causing an increase in temperature of gases. There are many thousands of different hydrocarbon fuel components, which consist mainly of hydrogen and carbon but may also contain oxygen, nitrogen, and/or sulphur, etc. The main combustible elements are carbon and hydrogen; another combustible element often present in fuels, although rather undesirable, is sulphur. The oxygen necessary for combustion is obtained from air, which is oxygen diluted chiefly by nitrogen COMPOSITION OF AIR: Table gives proportion of oxygen and nitrogen by volume as well as by mass of dry air. In combustion, oxygen is the reactive component of air. The properties of air vary geographically, with altitude and with time. It is usually sufficiently accurate to regard air as 21% oxygen and 79% inert gases taken as nitrogen (often called atmospheric nitrogen) by volume. Gas O2 N2 A CO2 Air Volume % 20.95 78.09 0.93 0.03 100.00 Mass % 23.16 75.55 1.25 0.04 100.00 Molar Mass 32.00 28.01 38.95 44.01 28.95 Molar Fraction 0.21 0.79 Molar Ratio 1 3.76

1.00

4.76

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1 0.21 = 3.76 For each mole of oxygen in air there are 0.21 moles of atmospheric nitrogen

The molar mass of air is obtained as 28.95 (usually approximated by 29) from the equation ~ where xi is the mole fraction defied as the number of moles of each component ni, divided by the total number of moles of mixture n. Because atmospheric nitrogen contains traces of other species, its molar mass is slightly different from that of pure molecular nitrogen, i.e. obtained from equation of state with universal gas constant Ro = 8314.3 J/kmol K and
3.482 10 3 p ( Pa ) kg / m = T(K) M = 28.95: . Thus the value for the density of dry air at 1 atmosphere (1.0133 105 Pa) and 25C is 1.184 kg/m3. M aN 2 = 28.95 .21 32 = 28.14 1 0.21 . The density of dry air can be M = 1 x ni M i = ~i M i n i i

Actual air normally contains water vapour, the amount depending on temperature and degree of saturation. Typically the proportion by mass is about 1 percent, though it can rise to about 4 percent under extreme conditions. The relative humidity compares the water vapour content of air with that required to saturate. It is defined as the ratio of the partial pressure of water vapour actually present to the saturation pressure at the same temperature.
STOICHIOMETRY

Most IC engines obtain their energy from the combustion of a hydrocarbon fuel with air, which converts chemical energy of the fuel to internal energy in the gases within the engine. The maximum amount of chemical energy that can be released (heat) from the fuel is when it reacts (combust) with a stoichiometric amount of oxygen. Stoichiometric oxygen (sometimes also called theoretical oxygen) is just enough to convert all carbon in the fuel to CO2 and all hydrogen to H2O, with no oxygen left over.
Stoichiometric Reaction: A stoichiometric reaction is defined such that the only products are carbon dioxide and water. The components on the left side of a chemical reaction equation which are present before the reaction are called reactants, while the components on the right side of the equation which are present after the reaction are called products or exhaust. Chemical equations are balanced on a basis of the conservation of mass principle (or the mass balance), which can be stated as follows: The total mass of each element is conserved during a chemical reaction. That is, the total mass of each element in the products must be equal to the total mass of that element in the reactants even though the elements exist in different chemical compounds in the reactants and products. Also, the total number of atoms of each element is conserved during a chemical reaction since the total number of atoms of an element is equal to the total mass of the element divided by its atomic mass. The total number of moles is not conserved during a chemical reaction.

In chemical reactions molecules react with molecules, so in balancing a chemical equation, molar quantities (fixed number of molecules) is used and not mass quantities. It is convenient to balance combustion reaction equations for one kmole of fuel. The energy released by the reaction will thus have units of energy per kmole
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of fuel, which is easily transformed to total energy when the flow rate of fuel is known. One kmole of a substance has a mass in kilograms equal in number to the molecular mass (molar mass) of that substance. Mathematically: m = NM [kmole] [kg/kmole] Where: m = mass [kg], N = number of moles [kmole], M = molecular mass [kg/kmole], 1 kmole = 6.02 1026 molecules. For example, the stoichiometric reaction of propane would be C3H8 + a O2 = b CO2 + d H2O Carbon balance gives: b = 3; Hydrogen balance gives: 2d = 8 d = 4; Oxygen balance gives: 2a = 2b + d a = 5. Then, reaction equation becomes C3H8 + 5 O2 = 3 CO2 + 4 H2O. Very small powerful engines could be built if fuel were burned with pure oxygen. However, the cost of using pure oxygen would be prohibitive, and thus is not done. Air is used as the source of oxygen to react with fuel. Nitrogen and argon are essentially chemically neutral and do not react in the combustion process. Their presence, however, does affect the temperature and pressure in the combustion chamber. Nitrogen usually enters a combustion chamber in large quantities at low temperatures and exists at considerably higher temperatures, absorbing a large proportion of the chemical energy released during combustion. When the products are at low temperature the nitrogen is not significantly affected by the reaction. At very high temperatures a small fraction of nitrogen reacts with oxygen, forming hazardous gases called NOx.
Stoichiometric Air/Fuel Ratio Stoichiometric (or chemically correct or theoretical) proportions of fuel and air are calculated from the stoichiometric reaction on molar basis. The stoichiometric Air to fuel ratio on molar basis is 4.76 = 4.76 ( + 0.5). The stoichiometric air/fuel (A/F)s or fuel/air (F/A)s ratios depend on fuel composition. Stoichiometric air/fuel (A/F) s on mass basis can also be calculated. Figure shows the variation in (A/F)s as the ratio of hydrogen to carbon (y = H/C) varies from 1 (e.g. benzene) to 4 (methane). The complete combustion of a general hydrocarbon fuel of average molecular composition CH with air would be CH + (O2 + 3.76 N2) = 1 CO2 + 2 H2O+ 3 N2
18

16 (A/F)s 14 12 1.0 2.0 3.0 4.0 Fuel molar H/C ratio

Carbon balance gives: 1 =; Hydrogen balance gives: 22 = 2 = 0.5; Oxygen balance gives: 2 = 21 + 2 = + 0.25;
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Nitrogen balance gives: 2(3.76) = 23 3 = 3.76( + 0.25).

Then, reaction equation becomes CH + ( + 0.25) (O2 + 3.76 N2) = CO2 + 0.5 H2O + 3.76( + 0.25) N2 This equation can also be written in the following form: CH/ + (1 + 0.25/) (O2 + 3.76 N2) = CO2 + (0.5/) H2O + 3.76(1 + 0.25 /) N2

It can be noted that only the ratios i.e., only the relative proportions on a molar basis are used. Thus the fuel composition could have been written CHy where y = /. The ratio / for the hydrocarbon CH used by the engine may not be known, but the ultimate analysis of the fuel gives the percentage by mass of Carbon, C, and
H 1.008 = hydrogen, H, and it is easy to see that C 12.01
1

M 28.95 A F = = 4.76 a = 4.76(1 + 0.25 y ) 12.01 + 1.008 y MF F s A s .

The molar masses of oxygen, atmospheric nitrogen, atomic carbon, and atomic hydrogen are respectively, 32, 28.16, 12.01, and 1.008. It can be noted that (A/F) s depends only on y, the ratio of hydrogen to carbon moles.
EXAMPLE-1

A hydrocarbon fuel of composition 84.1% by mass carbon, C, and 15.9% by mass hydrogen, H, has a molar mass of 114.15. Determine (a)the number of moles of (i) air required for stoichiometric combustion and (ii) products produced per mole of fuel; (b)(A/F)s and (F/A)s (c)the molar masses of the reactants and the products; (d)mole fractions of the product species. Ans. (a) (i) 59.5 (ii) 64 (b) 15.09; 0.066 (c) 30.36; 28.7 (d) 0.1250 CO2, 0.1406 H2O, 0.7344 N2
The complete combustion of a general fuel of molecular composition CHO N with air would be

CH O N + (O2 + 3.76 N2) = 1 CO2 + 2 H2O+ 3 N2

137.8 ( + 0.25 0.5 ) A = This gives F s 12.01 + 1.008 + 16 + 14.01 RICH MIXTURE REACTIONS

Fuel-air mixtures with more than or less than the stoichiometric air requirement can be burned. Combustion can occur, within limits, i.e., the proportions of the fuel and air must be in the proper range for combustion to begin. For example, natural gas will not burn in air in concentrations less than 5 percent or greater than about 15 percent. With excess air or fuel-lean combustion, the extra air appears in the products in unchanged form. With less than stoichiometric air requirement, i.e., with fuel-rich combustion, there is insufficient oxygen to oxidize the fuel fully C and H to CO2 and H2O. The products are a mixture of CO2 and H2O with carbon monoxide CO and hydrogen H2 (as well as N2). Carbon monoxide is a colourless, odourless, poisonous gas which can be further burned to form CO2. It is produced in any combustion
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process when there is a deficiency of oxygen. It is very likely that some of the fuel will not get burned when there is a deficiency of oxygen. This unburned fuel ends up as pollution in the exhaust of the engine. Because the composition of the combustion products is significantly different for fuel-lean and fuel-rich mixtures, and because the stoichiometric fuel/air ratio depends on fuel composition, the ratio of the actual fuel/air ratio to the stoichiometric ratio (or its inverse) is a more informative parameter for defining mixture composition. Various terminologies are used for the amount of air or oxygen used in combustion. 80% stoichiometric air = 80% theoretical air = 80% air = 20% deficiency of air; 120% stoichiometric air = 120% theoretical air = 120% air = 20% excess air
Fuel/Air Equivalence Ratio: For actual combustion in an engine, the fuel/air equivalence ratio is a measure of the fuel-air ( F / A) act ( A / F ) stoich = mixture relative to stoichiometric conditions. It is defined as: = ( F / A) stoich ( A / F ) act where: F/A = mf /ma = fuel-air ratio; A/F = ma /mf = air-fuel ratio; ma = mass of air; mf = mass of fuel

Relative Air/Fuel Ratio: The inverse of , the relative air/fuel ratio , is also sometimes used.

= 1 =

( F / A) stoich ( F / A) act

( A / F ) act ( A / F ) stoich

For fuel-lean mixtures: < 1, >1, Oxygen in exhaust For stoichiometric mixtures: = = 1, maximum energy released from fuel For fuel-rich mixtures: > 1, < 1, CO and fuel in exhaust
Lean or Rich Mixture Reactions: At low temperatures and reactant carbon to oxygen ratios less than one, the overall combustion reaction can be written as CH O N + ( / ) (O2 + 3.76 N2) = 1 CO2 + 2 H2O + 3 N2 + 4 O2 + 5 CO + 6 H2

For reactant carbon to oxygen ratios greater than one, we would have to add solid carbon C(s) and several other species. Convenient approximations for lean and rich combustion are > 1, 4 = 0; < 1 5 = 6 = 0
Lean Mixture Reactions: For the lean or stoichiometric cases, atom-balance equations are sufficient to determine the product composition (four equations and four unknowns)

For general fuel, fuel-lean combustion reaction can be written as:

CH O N + ( / ) (O2 + 3.76 N2) = 1 CO2 + 2 H2O + 3 N2 + 4 O2 EXAMPLE-2: Combustion of isooctane with 25% excess air or 1.25 times the stoichiometric air requirement ( = 0.8), C8H18 + (12.5 / 0.8) (O2 + 3.76 N2) = 8 CO2 + 9 H2O + 58.75 N2 + 3.125 O2 giving mole fractions

of product species as 0.1014 CO2, 0.1141 H2O, 0.7448 N2, 0.0396 O2

Rich Mixture Reactions:

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With fuel-rich combustion the product composition cannot be determined from an element balance alone and an additional assumption about the chemical composition of the product species must be made. If we assume that H2 is not present in the exhaust, as the reaction rate of hydrogen is faster than that of carbon, then atom balance equations would be sufficient to determine the product composition. EXAMPLE-3: Combustion of isooctane with 80% stoichiometric air ( = 1.25) C8H18 + (12.5 / 1.25) (O2 + 3.76 N2) = 3 CO2 + 9 H2O + 37.6 N2 + 5 CO

giving mole fractions of product species as 0.0549 CO2, 0.1648 H2O, 0.6886 N2, 0.0916 CO.
For the fuel-rich case, assuming equilibrium between the species CO2, H2O, CO and H2. The reaction relating these species (often called water gas reaction) would be CO2 + H2 CO + H2O

We introduce an equilibrium constant K for the reaction which is a function of temperature.

EXAMPLE-4 K (T ) =

2 5 1 6 K can be determined from a curve fit to JANAF table data:

In fuel-rich combustion product mixtures, equilibrium between species CO2, H2O, CO and H2 is assumed. For = 1.25, for C8H18air combustion products, determine the (a) mole fractions and (b) the mass fractions of the product species. (Assume equilibrium constant, K = 3.5) Ans. (a) 0.0839 CO2, 0.1359 H2O, 0.6886 N2, 0.0626 CO, 0.0289 H2 (b) 0.1356 CO2, 0.0898 H2O, 0.7081 N2, 0.0644 CO, 0.0021 H2
EXAMPLE-5

(a) For stoichiometric combustion of nitromethane, CH3NO2, find air/fuel ratio and mole fractions of the product species (b) If nitromethane burns without air compare its exhaust composition with that obtained from stoichiometric combustion. (Assume equilibrium constant, K = 3.5) Ans. (a) (A/F)s = 1.693; 0.1718 CO2, 0.2577 H2O, 0.5705 N2 (b) 0.0833 CO2, 0.2500 H2O, 0.1667 N2, 0.2500 CO, 0.2500 H2
EQUIVALENCE RATIO DETERMINATION FROM EXHAUST GAS CONSTITUENTS

Exhaust gas composition depends on the relative proportions of fuel and air fed to the engine, fuel composition, and completeness of combustion. These relationships can be used to determine the operating fuel/air equivalence ratio of an engine from knowledge of its exhaust composition. It is common practice to analyze the exhaust of an IC engine. Chemical composition of the hot exhaust is determined by various chemical, electronic, and thermal methods. This may be done by taking a sample of the exhaust gases and running it through an external analyzer. When this is done, there is a high probability that the exhaust gas will cool below its dew-point temperature before it is fully analyzed, and the condensing water will change the composition of the exhaust. To compensate for this, a dry analysis can be performed by first removing all water vapour from the exhaust, usually by some thermochemical means.
COMBUSTION EFFICIENCY:

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Even when the flow of air and fuel into an engine is controlled exactly at stoichiometric conditions, combustion will not be perfect, and components other than CO2, H2O, and N2 are found in the exhaust products. One major reason for this is the extremely short time available for each engine cycle, which often means that less than complete mixing of the air and fuel is obtained. Some fuel molecules do not find an oxygen molecule to react with, and small quantities of both fuel and oxygen end up in the exhaust. In practice, the exhaust gas of an internal combustion engine contains incomplete combustion products (e.g., CO, H2, unburned hydrocarbons, soot) as well as complete combustion products (CO2 and H2O). Under lean operating conditions the amounts of incomplete combustion products are small. Under fuel-rich operating conditions these amounts become more substantial since there is insufficient oxygen to complete combustion.

Combustion Efficiency

Com bustion efficiency as a function of fuel equivalnec ratio

100 90 (%) 80 70 60 50 0.4 0.6 0.8 1.0 1.2 1.4 1.6 Fuel E quivalence R atio
Fig 3
Lean

Because a friction of the fuels chemical energy is not fully released inside the engine during the combustion process, hence combustion efficiency is defined as the fraction of the fuel energy supplied which is released in the combustion process. Figure above shows how combustion efficiency varies with the fuel/air equivalence ratio for internal combustion engines. SI ENGINES HAVE COMBUSTION EFFICIENCEY in the range of 95% to 98% for lean mixtures. For mixtures where there is no enough to react all the fuel, the combustion efficiency steadily decreases as the mixture become richer combustion efficiency is little affected by other engine operating and design variables, provided the engine combustion process remains stable. CI engines always operate lean overall and typically have combustion efficiencies of about 98%. DISSOCIATION

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In actual engine performance the combustion usually is not complete even in the presence of excess air, because of dissociation at high temperature and also unsatisfactory mixing of the air and the fuel. When hydrocarbon fuels react with oxygen (air) at high engine temperatures (greater than about 2200 K), dissociation of
normally stable components can occur. CO2, dissociates to CO and O, O2 dissociates to monatomic O, N2 dissociates to N, etc. This does not only affect chemical combustion, but is a cause of one of the major emission problems of IC engines. Nitrogen as diatomic N2 does not react with other substances, but when it dissociates to monatomic nitrogen at high temperature it readily reacts with oxygen to form Nitrogen dioxide (NOx), a major pollutant from automobiles e.g., NO (Nitric oxide) and NO2 (Nitrogen dioxide). (Note: N2O is Nitrous oxide). In such cases the exhaust gases may contain certain percentages of CO, H2, NO, OH, H, O, and CH4. To avoid generating large amounts of nitrogen oxides, combustion temperatures in automobile engines are lowered, which reduces the dissociation of N2. Unfortunately, this also lowers the thermal efficiency of the engine. CHEMICALLY REACTING GAS MIXTURES The working fluids in engines are mixtures of gases. Depending on the problem under consideration and the portion of the engine cycle in which it occurs, chemical reactions may: (1)be so slow that they have a negligible effect on mixture composition (the mixture composition is essentially frozen); (2)be so rapid that the mixture state changes and the composition remains in chemical equilibrium; (3)be one of the rate-controlling processes that determine how the composition of the mixture changes with time. Chemical Equilibrium: It is a good approximation for performance estimates in engines to regard the burned gases produced by the combustion of fuel and air as in chemical equilibrium. It means that the chemical reactions, by which individual species in the burned gases react together, produce and remove each species at equal rates. No net change in species composition results. For example, if the temperature of a mass of CO2 gas in a vessel is increased sufficiently, some of the CO2 molecules dissociates into CO and O2 molecules. If the mixture of CO2, CO, and O2 is in equilibrium, then CO2 molecules are dissociating into CO and O2 at the same rate as CO and O2 molecules are recombining in the proportions required to satisfy the equation CO + O2 CO 2 Owing to the dissociation when carbon and hydrogen react with oxygen of air, the reaction does not proceed to the point where all carbon and hydrogen are consumed, forming CO2 and H2O. Instead, the reactions proceed only until an equilibrium condition is reached in which not only the final products of reaction, CO2 and H2O, are present, but also certain amounts of the original reaction substances and some intermediate compounds. The second law of thermodynamics defines the criterion for chemical equilibrium, in which minimization of Gibbs free energy is considered. Practical Chemical Equilibrium: Page 8 of 14

The proportions, at equilibrium, of the different constituents of the products of combustion depend on the original proportions and on the temperature and pressure reached at the end of the reaction. The higher the final temperature, the less complete the combustion reaction. On the other hand, the higher the pressure, the more complete the reaction. In fuel-air mixtures at equilibrium after combustion, the following substances usually are present: CO2, H2O, N2, O2, CO, H2, H, O, OH, NO, C, and CH4. However, free carbon, C, and methane, CH4, are present in such small portions that they can be disregarded. If we consider, H, O, OH and NO the only species of importance because of dissociation then the reaction equation can be written as: CH O N + ( / ) (O2 + 3.76 N2) = 1 CO2 + 2 H2O + 3 N2 + 4 O2 + 5 CO + 6 H2 + 7 H + 8 O + 9 OH + 10 NO

Atom balancing yields the four equations. Introduction of six equilibrium constants will yield ten equations for the ten unknowns. A solution can be obtained by solving these equations for the given fuel composition, fuel/air equivalence ratio, and product pressure and temperature.
Chemical Reaction Rates: Whether a system is in chemical equilibrium depends on whether the time constants of the controlling chemical reactions are short compared with time scales over which the system conditions (temperature and pressure) change. Chemical processes in engines are often not in equilibrium. Important examples on non-equilibrium phenomena are the flame reaction zone where the fuel is oxidized, and the air-pollutant formation mechanism. Such non-equilibrium processes are controlled by the rate at which actual chemical reactions which convert reactants to products occur. The rates at which chemical reactions proceed depend on the concentration of the reactants, temperature, and whether any catalyst is present. This field is called chemical kinetics. Unburned Mixture Composition: During the exhaust stroke of an engine, not all of the exhaust gases pushed out of the cylinder by the piston, a small residual being trapped in the clearance volume. The amount of this residual depends on the compression ratio, and somewhat on the location of the valves and valve overlap. The unburned mixture for a spark ignition engine during intake and compression consists of air, fuel, and previously burned gases. It is therefore, a mixture of CO2, H2O, N2, O2, CO, and H2 for fuel-rich mixtures, and fuel (usually vapour). The composition of the unburned mixture does not change significantly during intake and compression. It is sufficiently accurate to assume the composition is frozen. For the compression ignition engine, the unburned mixture prior to injection contains no fuel; it consists of air and previously burned gas. The combustion products or burned mixture gases, during the combustion process and much of the expansion process, are close to thermodynamic equilibrium. As these combustion products cool, recombination occurs. Towards the end of the expansion process, the gas composition departs from the equilibrium composition; recombinations no longer occur fast enough to maintain the reacting mixture in equilibrium. During the exhaust process, reactions are sufficiently slow so that for calculating thermodynamic properties the composition can be regarded as frozen. The mass of charge trapped in the cylinder (mc) is the inducted mass per cycle (mi), plus the residual mass (mr), left over from the previous cycle. The residual fraction (xr) is xr = mr / mc. Typical residual fractions in SI engines range from 20% at light load to 7% at full load. In CI engines the residual fraction is smaller ( a few percent) due to the higher compression ratio, and in naturally aspirated engines is approximately constant since the intake is unthrottled. If the inducted mixture is fuel and air (or air only), then the burned gas fraction (xb) in the unburned mixture during compression equals the residual fraction Exhaust Gas Recirculation: In some engines, a fraction of the engine exhaust gases is recycled to the intake to dilute the fresh mixture for control of NOx emissions. If the percent of exhaust gas Page 9 of 14

recycled (%EGR) is defined as the percent of the total intake mixture which is recycled exhaust, EGR (%) = mEGR / mi, where mEGR is the mass of exhaust gas recycled, then the burned gas fraction m EGR + mr EGR = (1 x r ) + x r . Up to about 30% of the exhaust can in the fresh mixture is xb = mc 100 be recycled; the burned gas fraction during compression can, therefore, approach 30 to 40%. Heat Of Combustion: From steady-flow energy balance equation with no work interaction heat liberated by the combustion reaction of a hydrocarbon fuel with air is the difference between the total enthalpy of the products and the total enthalpy of the reactants. This is called heat of reaction, enthalpy of reaction, heat of combustion, or enthalpy of combustion and is given by: Q = N i hi N i hi

Where: Ni = number of moles of component i, hi = ( h f ) + hi , h f = enthalpy of formation, the enthalpy needed to form one mole of that component at standard conditions of 25C and 1 atm, hi = change of enthalpy from standard temperature for component i. Q will be negative, meaning that heat is given up by the reacting gases.
0 0

PROD

REACT

Values of h f and h are molar-specific quantities and can be found in tables. The enthalpy of combustion of a particular fuel will be different at different temperatures and pressures.
EXAMPLE-7

Evaluate the lower heating value per unit mass of stoichiometric mixture and per unit volume of stoichiometric mixture (at standard atmospheric conditions) for isooctane. Assume the fuel is fully vaporised. Lower heating value of isooctane (C8H18) is 44.3 MJ/kg. (Ans. 2.75 MJ/kg; 3.41 MJ/m3)

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COMBUSTION TEMPERATURE One of the most important criteria in an engine is the combustion temperature (and hence pressure). Figure shows the temperatures reached on the combustion of mixtures of fuel and air of different strengths between 50% weak and 50% rich, for a compression ratio of 5/1 of an SI engine. The maximum temperature should theoretically be produced by stoichiometric mixture strength, but in fact it occurs at about 20% rich. The shape of the temperature curve is due to the dissociation of CO2 and H2O into CO, H2, and O2 which is slight at a temperature of 2000C, but increases rapidly above that. In engine combustion the dissociation of CO2 affects engine behaviour more than that of H2O which is relatively slight.

Fig 4

fig 5

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Combustion theory allows the dissociation proportions of CO, H2, and O2 to be calculated and represented in the combustion equations. Hence the energy released on combustion can be calculated. If the formation of nitric oxide which occurs at the higher temperatures is taken into account the temperatures attained are even lower, due to the absorption of energy to form NO as shown in Fig 4 above.

At the higher compression ratios of modern engines higher temperatures and pressures are attained and dissociation occurs, not only to a greater extent for NO, but also to some common radicals mainly OH, H, and O, e.g. at 3000C a stoichiometric mixture of octane and air at equilibrium will contain OH (1.4%), H (0.3%), O (0.3%), and NO (0.3%). Mixture strength, particularly for a spark-ignited engine, can vary considerably due to the way in which the mixture is created and distributed. It is not a controlled process as it is in the diesel engine. The maximum temperature in a combustion chamber can be controlled by adjusting the amount of excess air, which serves as a coolant. SELF-IGNITION TEMPERATURE Bringing a fuel into intimate contact with oxygen is not sufficient to start a combustion process. The fuel must be brought above its ignition temperature (also called self-ignition temperature) to start the combustion. If the temperature of an air-fuel mixture is raised high enough, the mixture will self-ignite without the need of a spark plug or other external igniter. This is the basic principle of ignition in a compression ignition engine. The compression ratio is high enough so that the temperature rises above self-ignition temperature (SIT) during the compression stroke. Self-ignition then occurs when fuel is injected into the combustion chamber. On the other hand, self-ignition (pre-ignition or autoignition) is not desirable in an SI engine, where a spark plug is used to ignite the air-fuel at the proper time in the cycle. The compression ratios of gasolinefueled SI engines are limited to about 11:1 to avoid self-ignition. Table gives minimum ignition temperatures of various substances in atmospheric air. Fuel SIT ( C) 580 630 515 610 480 260 210 210 365 385

Hydrogen Methane Ethane CO Propane Gasoline Kerosine Diesel Ethanol Methanol

SELF-IGNITION Figures a, b, c show the pressure-time history within a cylinder of a typical SI engine.

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Fig 6 (a,b and c) With no self-ignition the pressure force on the piston follows a smooth curve, resulting in smooth engine operation (Fig.6 a). When self-ignition does occur, pressure forces on the piston are not smooth and engine knock occurs (Fig.6 b & c). The combustion process is a fast exothermic gasphase reaction (where oxygen is usually one of the reactants). A flame is a combustion reaction which can propagate subsonically through space; motion of the flame relative to the unburned gas is the important feature. The existence of flame motion implies that the reaction is confined to the zone which is small in thickness compared to the dimensions of the apparatus in our case the engine combustion chamber. Appendix

Element C H O N

Molar Mass 12.010 1.008 16.00 14.01

Fuel Name Coal (Carbon) Hydrogen Carbon monoxide Methane Nitromethane Methanol Ethanol Propene Propane Butane Toluene Triptane Heptane Gasoline Isooctane Isodecane Cetane

Fuel Formula C H2 CO CH4 CH3NO2 CH4O C2H6O C3H6 C3H8 C4H10 C7H8 C7H16 C7H16 C8H15 C8H18 C10H22 C16H34

Lower Heating Value (MJ/kg) 33.80 120.00 10.10 50.00 10.92 20.05 26.95 48.95 46.19 49.56 40.60 44.44 44.56 43.00 44.30 44.22 43.98

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Reference 1. J.B. Heywood, Internal Combustion Engine Fundamentals, McGraw Hill International Editions, 1989. 2. B. P. Pundir, Engine Emissions: Pollutant Formation and Advances in Control Technology, Narosa Publishing House, New Delhi, 2007. 3. Handbook of Air Pollution from Internal Combustion Engines: Pollutant Formation and Control, Ed. Eran Sher, Academic Press, 1998.

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